Optical Absorption and Photoluminescence of Single-Layer Boron Nitride from a First-Principles Cumulant Approach

Abstract

The photoluminescence spectrum of a single-layer boron nitride remains elusive, marked by enigmatic satellites that hint at significant but unidentified exciton–phonon coupling. Here, by employing a first-principles approach based on the many-body cumulant expansion of the charge response, we calculate the optical absorption and photoluminescence of a single-layer boron nitride. We identify the specific exciton–phonon scattering channels and unravel their impact on the optical absorption and photoluminescence spectra, thereby providing an interpretation of the experimental features. Finally, we show that, even in a strongly polar material such as h-BN monolayer, the electron–hole interaction responsible for the excitonic effect results in the cancellation of the Frölich interaction at small phonon momenta. This effect is captured only if the invariance of the exciton–phonon matrix elements under unitary transformations in the Bloch function manifold is preserved in the calculation.